Diazoamino compound



Patented Sept. 19, 1939 UNITED STATES PATENT OFFICE DIAZOAMINO COMPOUND Albert Schmelzer, Cologne, and Eberhard Stein, Leverkusen Schlebusch, Germany, assignors to General =Aniline Works, Inc., New York, N, Y.,

a corporation of Delaware No Drawing. Application November 26, 1938, Se-

it relates to compounds of the following general formula X stands for an acid salt-forming group and n for one of the numbers 1 and 2.

Our new diazoamino compounds can be ob- 1 tained in the usual manner, for instance, by reacting diazo compounds of aromatic amines with a compound of the following formula i CH-Nalkylene-X /CH2 S02 wherein X means the same as stated above. As

aromatic diazo compounds preferably such are used as are free from carboxylic and sulfonic groups.

Our new diazoamino compounds are obtained generally as colorless to yellowish to brown crystals.

By the addition of acids or salts of acid action the new diazoamino compounds are split up into the starting components, i. e. into a diazo or tetrazo compound and into the stabiliser of the above Formula 2. The diazoamino compounds can, therefore, be employed in the preparation of azodyestuffs according to U. S. Patents 1,882,560 and 1,882,561.

The stabilisers used for the preparation of the diazoamino compounds are obtainable by reacting 3-tetramethylenesulfone-amine (obtained for instance according to application Ser. No.

186,085, filed January 21, 1938) with halogen-' alkylcarboxylicor halogenalkylsulfonic acids.

. According to the process in which the new.

i In this formula R stands for an aromatic radical,

In Germany December 1,

242,575 (application of even date entitled Process and preparations for the manufacture of a20- dyestuffs) they may be used in the form of salts with volatile bases; in processes where the presence of substances of buffer-action is desired they may be employed for instance in the form of magnesium salts.

The following examples illustrate the invention without, however, restricting it thereto, the parts being by weight.

Example 1 28.6 parts of 4-ch1oro-2-toluidine are finely suspended with 200 partsof Water and 77 parts of crude hydrochloric acid and at l0-12 C. diazotised with a solution of 14.3 parts of sodium nitrite in 30 parts of water. The filtered diazo solution is added drop by drop at a temperature below 10- C. to a'solution of 42.5 parts of 3-tetramethylenesulfone-glycine of the .formula CH2-O H-NH. CH2. 0 O O I CH2 CH2 is filtered off and dried in the drying oven at 40 C. The compound is colorless."

I Example 2 A 61.6 parts of 2.5 diethoxy-4-benzoylamino-1- amino-benzeneare suspended in parts of water and parts of crude hydrochloric acid and diazotised at 20-25 C. with 17.9 parts of sodium nitrite in 45 parts of water. The filtered diazo solution is added drop by drop at a temperature.

below 10 C. to a solution of 42.5 parts of 3-tetramethylenesulfoneglycine and 60 parts anhydrous sodium carbonate in 300 parts of water. After 16 hours stirring the coupling is complete. The diazoamino compound of the following formula OO.CnHu

CHz-CHz is sucked off and dried in the drying oven at 40 C. The compound shows a brownish col oration.

Example 3 If in Example 2 instead of 3-tetramethylensulfone-glycine 53.5 parts of B-tetramethylenesulfone-taurine are used the diazoamino compound of the following formula err-0H2 OzHr CH2CH2 CsHs. O

is obtained.

Example 4 following constitution S03 31 z-CH2 1 has separated.

If instead of 4-chloro-2-toluidine 5-ch1oro-2- toluidine is used the diazoamino compound of the following constitution is obtained CH-CH: Mg C1 CHz--C1H2 2 Example 5 31.8 parts of para-toluidine are suspended in 140 parts of water and 113.5 parts of crude hydrochloric acid and diazotised below C. with 21.5

parts of sodium nitrite in 45 parts of water. The diazo solution is filtered and added drop by drop to a solution of 64 parts of 3-tetramethylenesulfoneglycine and 115 parts of ammonium carbonate. in 330. parts of water. After 20 hours stirring the precipitated diazamino compound of the following constitution CHI-CH2 CH is sucked off and dried as usual. is weakly yellowish colored.

Example 6 The compound (EH-CH1 Mg CH:-

/SO2 CHPCHQ 2 Example 7 82 parts of 2-methoXy-4-benzoylamino-5- methyl-l-aminobenzene are suspended in 300 parts of water and 113.5 parts of crude hydrochloric acid and diazotised at -20 C. with 26.4 parts of sodium nitrite dissolved in 60'parts of water. The filtered diazo solution is added drop by drop at 1020 C. to a solution of 64 parts of 3-tetramethylenesulfoneglycine and 60 parts of anhydrous sodium carbonate in 100 parts of water while stirring well. After about 18 hours stirring the diazoamino compound is salted out by adding 250 parts of sodium chloride; the diazoamine compound shows a faint brownish coloration and corresponds to the following constitution NH CH--CH2\ S O: C O

| CH; Hz-CH: 0 11;

Example 8 The diazo solution prepared according to Example 5 is added drop by drop at a temperature below 10 C. to a. solution of 64 parts of 3-tetramethylenesulfone glycine and 60 parts of anhydrous sodium carbonate in 350 parts of water. After about hours stirring the diazoamino compound of the following constitution CHais salted out by adding 150 parts of sodium chloride. It is sucked off and dried as usual. The compound is faintly yellowish colored.

Example 9 77.1 parts of Z-amino-l-methoxybenzenelsulfodiethylamide are dissolved in 280 parts of Hr-CH:

20 is sucked ofi, washed with 1000 parts of a saturated sodium chloride solution and dried at 40 C.

We claim: 1. As new products diazoamino compounds of the general formula wherein R stands for an aromatic radical, free from carboxylic and sulfonic groups, X stands for an acid salt forming group and n for one of the numbers 1 and 2.

2. As new products diazoamino compounds of the general formula R N=NN-CHa. c o H OH-CH2 /S 0: HI-CHQ wherein R stands for an aromatic radical, free from carboxylic and sulfonic groups, and n for one of the numbers 1 and 2.

3. As new products diazoamino compounds of the general formula R N=N--NCH|.OHr-S 0.11

SO: CHI-CHI 91 wherein R. stands for an aromatic radical, free from carboxylic and sulfonic groups, and n for one of the numbers 1 and 2.

ALBERT SCHMELZER. EBERHARD STEIN. 

